a

Original Article http://dx.doi.org/10.4322/2176-1523.1310

OBTAINING NIOBIUM OXIDES IN ACETIC ACID WITH

ADDITION OF HF
Patrícia Marcolin 1
Marielen Longhi 2
Letícia Caio 3
Lucas Pandolphi Zini 3
Lilian Vanessa Rossa Beltrami 4
Jéssica Cristina Silva 5
Fernando Dal Pont Morisso 5
Sandra Raquel Kunst 1
Cláudia Trindade Oliveira 5

Abstract

During anodizing, the chemical attack of hydrofluoric acid (HF) electrolytes on niobium can promote the formation
of oxides with porous structures. However, this chemical attack can also cause an intense dissolution of the oxide during its
formation. This effect can be minimized by varying the HF concentration of the anodizing electrolyte, thereby controlling
the growth of the porous oxide. Studies have alternative electrolytes that do not use HF to obtain porous oxides.
Thus, organic electrolytes, such as acetic acid, may be a viable alternative. In this context, the objective of this study is to
obtain and evaluate the anodization of niobium in acetic acid at different current densities (10, 20 and 50 mA/cm2) and to
study the influence of the addition of HF to the electrolyte. The results showed that the anodized anodic in acetic acid,
under conditions of 100 V and 10 mA/cm2, presented porous oxide with less defects. Therefore, this result indicates that
it is possible to produce porous niobium oxides by anodizing in HF-free electrolyte.
Keywords: Niobium; Anodizing; Acetic acid.

OBTENÇÃO DE ÓXIDOS DE NIÓBIO EM ÁCIDO

ACÉTICO COM ADIÇÃO DE HF

Resumo

Durante a anodização, o ataque químico de eletrólitos de ácido fluorídrico (HF) sobre o nióbio pode promover a
formação de óxidos com estruturas porosas. Contudo, este ataque químico pode causar uma intensa dissolução do óxido
durante sua formação. Esse efeito pode ser minimizado variando-se a concentração de HF do eletrólito de anodização,
controlando assim o crescimento do óxido poroso. Estudos têm buscado por eletrólitos alternativos que não utilizam
HF na obtenção de óxidos porosos. Logo, eletrólitos orgânicos, como o ácido acético, podem ser uma alternativa viável.
Neste contexto, o objetivo deste estudo é obter e avaliar a anodização de nióbio em ácido acético em diferentes densidades
de correntes (10, 20 e 50 mA/cm2) e estudar a influencia da adição de HF ao eletrólito. Os resultados mostraram que
a amostra de nióbio anodizada em ácido acético, nas condições de 100 V e 10 mA/cm2, apresentou óxido proroso com
menor quantidade de defeitos. Portanto, este resultado indica que é possível a formação de óxidos de nióbio porosos por
anodização em eletrólito livre de HF.
Palavras-chave: Nióbio; Anodização; Ácido acético.

Programa de Pós-graduação em Engenharia de Processos e Tecnologias – PGEPROTEC, Universidade de Caxias do Sul – UCS, Caxias do Sul, RS,
1

Brazil. E-mail: pmarcolin@ucs.br

Programa de Pós-graduação em Engenharia de Minas, Metalúrgica e de Materiais – PPGE3M, Universidade Federal do Rio Grande do Sul – UFRGS,
2

Porto Alegre, RS, Brazil.

Laboratório de Corrosão – LCOR, Universidade de Caxias do Sul – UCS, Caxias do Sul, RS, Brazil.
3

Laboratório de Pesquisa em Corrosão – LAPEC, Universidade Federal do Rio Grande do Sul – UFRGS, Porto Alegre, RS, Brazil.
4

Instituto de Ciências Exatas e Tecnológicas – ICET, Universidade Feevale, Novo Hamburgo, RS, Brazil.
5

2176-1523 © 2016 Associação Brasileira de Metalurgia, Materiais e Mineração. Publicado pela ABM. Este é um artigo de acesso
aberto distribuído sob os termos da licença Creative Commons CC BY-NC-ND (Attribution-NonCommercial-NoDerivs) - https://
creativecommons.org/licenses/by-nc-nd/4.0/.

Tecnol. Metal. Mater. Miner., São Paulo, v. 15, n. 1, p. 35-42, jan./mar. 2018 35
Marcolin et al.
1 INTRODUCTION
Metals that form an oxide layer through anodizing
are classified as metal valve. Anodizing is an ideal process
for creating fine and homogeneous oxide layers with good
dielectric and semiconductor properties. It oxidizes in
temperatures above 200°C. Its most common oxidation states
are 2+, 4+ and 5+. Niobium oxide (II) presents superconductivity
in temperatures near absolute zero and is used in circuits
as resistor. The oxide with oxidation number 4+ acts as an
excellent semiconductor. However, Nb2O5 is the most stable
compound and demonstrates good corrosion resistance in
acid and basic environments, high refractive index and low
absorption in UV-visible region [1,2].
Anodization allows the formation of two types of
oxides: barrier and porous. The barrier oxides are obtained
in electrolytes that do not attack it [1,3]. While porous oxides
are formed in electrolytes that chemically attack the oxide.
In this process, first the barrier oxide is formed, followed
by dissolution of the same, which gives rise to the pores.
This dissolution occurs by migration of the acid anion into
the oxide film, forming a complex with the metal, which
is soluble in water and responsible for pore formation [4].
Due to its biocompatibility and osteoconductivity,
this oxide class has potential application in the area of
nanobiotechnology, due to the control of pore formation,
such as size and uniformity, which favor cell growth [5,6].
Niobium can be applied in production of nanotubes,
nanowires and membranes. In form of oxide, niobium can
be used in gas sensors, solar cells, implants, electronic and
magnetic devices and biotechnology [7].
These oxides are obtained through an anodizing process
and may form barrier and porous oxides. Barrier oxides
are obtained in electrolytes that does not attack the oxide.
The electrolytes used for anodizing are generally acid,
because they present better results [1,3].
The excellent corrosion resistance of niobium in many
environments is attributed to the presence of a superficial
film of stable oxide (Nb2O5), protector and strongly adherent.
In front of their applicability and high corrosion resistance,
despite its relatively high cost, niobium is a material that has
stood out in the scientific and technologic landscape [8].
The choice of the appropriated material for equipment,
projects and controlled operations, constitute the largest
controlling weapons of corrosive process. Niobium, being a
very corrosion resistant in various environments, becomes
a promising material for many segments of industries. Some
studies related to pure niobium behavior and its alloys
in various environments were published. Most of them
show the good corrosion resistance, especially in aqueous
environments [1,3].
Currently, the formation of porous structures in
niobium occurs very efficiently in electrolytes containing
hydrofluoric acid (HF), that may cause an intense dissolution.
Meanwhile, in a controlled manner, through this dissolution
oxide can be obtained [7]. Considering the harmfulness of HF,
studies are being performed with organic electrolytes, such
as acetic acid, to form porous oxide with orderly growth.
36
In this context, in order to obtain continuous oxides
and with uniform pores, the objective of this study is to
promote the anodization of niobium in the acetic acid
electrolyte and to evaluate the influence of different current
densities and the concentration of HF in the electrolyte.
2 EXPERIMENTAL
Pure niobium (99.5%) was provided in form of plates
by Companhia Brasileira de Metalurgia e Mineração (CBMM).
Samples were analyzed for anodizing curves. Morphology
and deposited film thickness were evaluated by scanning
electron microscopy (SEM).
Samples were cut into the dimensions of 2.0 x 1.0 cm
and, posteriorly, drilled on one end for securing the electric
contact. Electrical insulation was made, leaving an exposed
area of 1cm2 on each side of the sample.
Samples was pickling in solution of hydrofluoric acid
(HF) 40% and nitric acid (HNO3) 60% during 5 minutes,
with stirring. Afterwards, they were rinsed with deionized
water and dried with cold air. On the anodizing process was
used the equipment brand Minipa model MPL-3303 with a
voltage source 300 V and 0.5 A, which was connected to a
computer for data acquisition. Potential was chosen in order
to force occurring of breakdown, to characterize the samples
to the edge of barrier oxide formation. Variations of current
densities used were 10, 20 and 50 mA/cm2. Table 1 shows the
nomenclature used for the samples analyzed in this research
and process parameters are described in Tables 2, 3 and 4.
For scanning electron microscopy, it was used an
equipment Jeol JSM-6510LV Scanning Electron Microscope.
Samples were analyzed in top view in order to obtain
information related to the morphology of the oxide formed
on the substrate surface. Samples were also evaluated
through cross section, with metallization with golden film.
Oxide densities of anodized samples were calculated
based on niobium oxide thicknesses and on anodizing
curves, according to Equation 1, through Faraday Law.
Calculated values are listed on Table 5.
itM
ρ= (1)
zFD
Where:
ρ = density (g/cm3);
i = current density (A/cm2);
t = time that i remains constant (s);
M = Nb molar mass (265,81 g/mol);
z = 10, product of niobium and oxygen oxidation states;
F = Faraday constant (9,64x10−4 C/mol);
D = thickness (cm).
Oxide production rate was calculated through
Equation 2. The values are listed on Table 4.
Thickness
Oxide production rate = (2)
Timeto reach100V
Tecnol. Metal. Mater. Miner., São Paulo, v. 15, n. 1, p. 35-42, jan./mar. 2018
 Obtaining Niobium oxides in acetic acid with addition of HF

Table 1. Samples and anodizing conditions 3 RESULTS AND DISCUSSION

Sample Current Applied
Electrolyte density Potential Figure 1 illustrates the scheme of different regions
(mA/cm2) (V) present on the potential versus time transients during
Nb 0 -- 0 0 niobium anodizing. And the Figure 2 shows potential and
Nb 1 Acetic acid 1 mol/L 10 300 current transients measured during anodizing in acetic acid
Nb 2 Acetic acid 1 mol/L 20 300 1 mol/L, 300 V and 10, 20 and 50 mA/cm2.
Nb 3 Acetic acid 1 mol/L 50 300 Region 1 (Figure 1 and 2), shows a linear increasing of
Nb 4 Acetic acid 1 mol/L 10 100 potential in function of time, generating a constant (∂V/∂t),
Nb 5 Acetic acid 1 mol/L + HF 0.01 mol/L 10 100 designated anodizing rate. In this region, it is observed a
Nb 6 Acetic acid 1 mol/L + HF 0.1 mol/L 10 100 characteristic behavior of barrier film formation wherein all
Nb 7 Acetic acid 1 mol/L + HF 1 mol/L 10 100
the current density is used for film formation. ∂V/∂t variation
remains constant until reach the dielectric breakdown
potential (Vb), wherein occurs a decrease of ∂V/∂t value,
showing the beginning of region 2 (Figure 1 and 2). As the
Table 2. Potential variation in function of time during anodizing
(acetic acid 1 mol/L, 300 V) Figure 2, the largest potential value is for the anodized sample
in 50 mA/cm2. This variation in ∂V/∂t, from region 1 to region
Sample ∂V/∂t (V/s) Vb (V)
2, has been already observed in other metals when anodized,
Nb 1 (10 mA/cm2) 2.22 275
characteristic of the dielectric breakdown beginning [1,9].
Nb 2 (20 mA/cm2) 3.45 275
Nb 3 (50 mA/cm2) 9.54 300
Region 2 is characterized by presenting a potential almost
constant [9].
∂V/∂t values measured for anodized Nb in the different
current densities are shown on Table 2.
Table 3. Oxide growth rate in niobium samples at 10 mA/cm2 and 100 V According with Table 2, despite the anodizing have been
Sample ∂V/∂t (V/s) made at 300 V, only the sample at 50 mA/cm2 demonstrated
Nb 4 1.84
breakdown potential of 300 V, being accompanied by oscillations
Nb 5 3.45 in the current density, characteristics of breakdown. The other
Nb 6 2.10 samples showed breakdown potential around 275 V, not
Nb7 1.27 being possible to identify oscillations in the current density.
This indicates that increasing of current density promotes
formation of an oxide with a higher growing rate and,
consequently, higher dielectric breakdown potential.
Table 4. Production and dissolution rate, ∂V/∂t, time to reach 100 V Niobium films, grown with higher ∂V/∂t, presented
and thickness, values obtained from cross section of the samples larger probability of defects formation than the formed with
lower ∂V/∂t. This could explain the higher Vb obtained in
Thickness at

rate (nm/s)

rate (nm/s)
5 min (nm)

production

this sample of 50 mA/cm2 and the observed oscillations [10].

dissolution
reach 100
Time to
Sample

Oxide

Oxide
V (s)

Nb4 57 560 10.98 -

Nb5 22 301 13.68 -
Nb6 50 301 6.02 7.66
Nb7 85 481 5.65 8.03

Table 5. Densities for oxides formed at 10 mA/cm2, acetic acid 1 mol/L,

with and without HF
Samples

Time to reach
Thickness (cm) Vb and stabilize Density (g/cm3)
potential (s)
Nb4 0.560x10−4 57 2.8066
Nb5 0.301x10−4 22 2.0153
Nb6 0.301x10−4 50 4.5803
Figure 1. Illustrative scheme of different regions present in potential
Nb7 0.481x10−4 85 4.8726 transients versus time graphs of Figure 1 during niobium anodizing.

Tecnol. Metal. Mater. Miner., São Paulo, v. 15, n. 1, p. 35-42, jan./mar. 2018 37
Marcolin et al.
Towards the context of this study, it was decided
to anodize niobium at 10mA/cm2, to ensure the oxide
formation with lower quantity of defects and at a potential
lesser than 300 V, avoiding occurrence of sparking. Is was
also noticed the formation of porous oxides by adding HF
to the electrolyte.
Figure 3 illustrates potential and current
transients of niobium anodized with acetic acid 1 mol/L,
at 10 mA/cm2 and 100 V, without adding HF and with
additions of 0.01, 0.1 and 1 mol/L of HF. All the samples
demonstrated similar behaviors, beginning with a linear
increasing of potential, wherein current density remains
constant at 10mA/cm2. After reaching potential of 100 V,
the samples preserve the potential constant and there is an
abrupt decrease of the current density, indicating the end
of film formation. In this case, it cannot be said that film
formation is completely barrier, once the addition of HF
induces the formation of a porous film.
Table 3 shows the growth rate of oxides formed
with and without addition of HF. According with Table 3,
Figure 2. Potential and current transients in function of time, measured during niobium anodizing in 10, 20 and 50 mA/cm2, at 300 V in acetic acid 1 mol/L.
Figure 3. Potential and current transients versus time for anodized niobium at 100 V in acetic acid 1 mol/L with and without adding of HF.
38
the increase of HF concentration decreases the growth rate
of oxide. It was observed a similar behavior with addition of
HF in oxalic acid in niobium anodizing, wherein HF induces
the dissolution of the oxide. The dissolution process occurs
concurrently with the barrier oxide formation, being directly
proportional to the increase of HF concentration. Figure 4
exemplifies the occurrence of this factor.
In Figure 4, the steps of formation refer to the
niobium oxide formation without addition of HF, where
it is noticed the continuous growth of the niobium oxide.
The sequence illustrated in the entire figure refers to the
oxide film formation and dissolution, which elucidates the
observed low anodizing rate [4].
Figure 5a-c show the micrographs in top view
and cross section of the anodized samples in acetic acid
1 mol/L, at 300 V and 10, 20 and 50 mA/cm2. It is seen,
in these samples, an irregular surface with imperfections,
which become more evident with increasing of current
density. The sample obtained at 10 mA/cm2 demonstrates,
Tecnol. Metal. Mater. Miner., São Paulo, v. 15, n. 1, p. 35-42, jan./mar. 2018
 Obtaining Niobium oxides in acetic acid with addition of HF

Figure 4. Dissolution model of niobium oxide formed in acetic acid with addition of HF.

Figure 5. (a) Micrograph of Nb2 sample: (a1) top view and (a2) cross section; (b) Micrograph of Nb2 sample: (b1) top view and (b2) cross
section; (c) Micrograph of Nb3 sample: (c1) top view and (c2) cross section.

Tecnol. Metal. Mater. Miner., São Paulo, v. 15, n. 1, p. 35-42, jan./mar. 2018 39
Marcolin et al.

besides imperfections, the formation of pores, like pits on
the niobium surface.
The occurrence of breakdown can also manifest in
form of random pits on the surface of anodized sample.
With increasing of current density and, consequently, with
the increase of electrons amount for oxide formation, located
points of occurrence of breakdown are noticed clearly.
The pores are scattered by the sample surface,
covering it completely, presumably by the increase of current
density values [11].
Figure 6 a-d, show the SEM micrographs of anodized
samples in acetic acid 1 mol/L, at 100 V and 10 mA/cm2,
without HF and with HF in concentrations of 0.01, 0.1 and
1 mol/L.

Figure 6. (a) Micrograph of Nb4 sample: (a1) top view and (a2) cross section; (b) Micrograph of Nb5 sample, obtained in acetic acid
1 mol/L + HF 0.01 mol/L at 100 V for 5 minutes: (b1) top view and (b2) cross section; (c) Micrograph of Nb6 sample: (c1) top view and
(c2) cross section; (d) Micrograph of Nb7 sample: (d1) top view and (d2) cross section.

40 Tecnol. Metal. Mater. Miner., São Paulo, v. 15, n. 1, p. 35-42, jan./mar. 2018

The sample in presence of acetic acid showed pores
on substrate surface, however, the oxides formation occurs
generally in environments containing strong electrolytes
able to attack chemically the substrate. Specifically, in case
of niobium, porous oxide formation occurs in electrolytes
that contain HF or at pH=14 [12]. The formation in
presence of an organic electrolyte, acetic acid in this case,
occurs probably because there is a small amount of oxygen
compared to aqueous solutions, thus favoring the oxide
chemical dissolution in function of oxide formation [13].
In acetic acid, the maximum thickness of an intact
anodic film is less than 25 nm, and thicker films, obtained
at higher potentials, contain imperfections in their pit
appearance morphology [14]. It has been reported that
anodizing in organic electrolyte produces very smooth curves
of anodizing, without any fluctuations in the current, which
was attributed to the low concentration and diffusivity of
ions in the organic electrolyte [15]. An organic electrolyte
has a small amount of oxygen compared to an aqueous
solution and therefore the chemical dissolution of the oxide
in an organic electrolyte depends on the water content [16].
Consequently, for the formation of porous oxides in the
form of nanotubes, a thicker layer of nanotubes will form
over a long time in an organic electrolyte, and the viscosity
of the electrolyte, whether under agitation or not and
the content of H2O, may influence the Formation of the
nanotube [17].
With addition of 0.01 mol/L of HF, there is pores
formation with less intensity. Therefore, the addition of
HF induces the pores formation and acetic acid inhibits the
dissolution process. The gradual increase of pores on the
samples is proportional to the increase of HF concentration,
however the oxides formed in organic electrolytes were
irregular.
Through time and thickness values showed on
Table 5, the oxide production rate can be calculated by
the Equation 2.
To calculate the oxide formation rate, only the
thicknesses of oxides formed until 300 s were used, and
the growth of the oxide layer after the time de potential
reached 100 V was not considered significant.
According to Table 4, it is observed that occurs
an increase of the oxide production rate with addition
of HF 0.01 mol/L to the electrolyte of anodizing – acetic
acid 1 mol/L. This corresponds to the obtained results for
the anodized sample in acetic acid 1 mol/L, in which occurs
pores formation and consequent oxide dissolution.
Comparing only the anodized samples containing
HF, it is noticed that the increase of HF concentration raises
REFERENCES
1 Graça MPF, Saraiva M, Freire FA, Valente MA, Costa LC. Electrical analysis of niobium oxide thin films. Thin Solid
Films. 2015;585:95-99.
Tecnol. Metal. Mater. Miner., São Paulo, v. 15, n. 1, p. 35-42, jan./mar. 2018
Obtaining Niobium oxides in acetic acid with addition of HF
the oxide dissolution rate, favoring the formation of porous
oxide. According to Figure 6a2, b2, c2 and d2, oxides cross
sections present homogeneous aspect.
To calculate oxide density, only the samples
that were not submitted to dieletric breakdown were
considered. It was utilized the oxides thickness described
on Table 5 to calculate the oxide density. The oxides
densities can have varied from 2 g/cm3 to 4 g/cm3, with
variation in the thickness of formed oxide, as reported in
another study in which they performed the anodization
of niobium to assess their anodic behavior, and found
density values close to 4 g/cm3 [12,18]. It is observed in
Table 5 that the oxide formed without presence of HF
presents value inferior to 4 g/cm3. According to Figure 6
(a1) this oxide is of the porous type, which would explain
the low density. However, for the oxides obtained
with addition of HF, the oxide density increased with
the decrease of the HF concentration. In addition, the
increase in HF concentration formed oxides with lower
∂V/∂t, consequently with fewer defects [10]. Since HF
causes the oxide to dissolve during its formation, this
would cause oxide formation to occur in a slower way,
therefore with less defects and higher density, which
agrees with the model suggested in Figure 4.
4 CONCLUSIONS
The formation of niobium oxides in acetic acid only
occurs efficiently with the application of lower current density
(10 mA/cm2). During the anodizing process, it was observed
that the lower breakdown potential and lower ∂V / ∂t resulted
in the formation of oxide with less defects.
In addition, the porous niobium oxide formation
was obtained by anodization using the 1 mol/L oxalic acid
solution under the conditions of 100 V and 10 mA/cm2
as the electrolyte. This result indicates that it is possible
to obtain porous niobium foams in free HF electrolytes.
However, the addition of HF to the electrolyte favors the
formation of porous oxide, where the dissolution process
is more intense for higher concentration of HF (1 mol/L).
Despite this, the oxide obtained in 1 mol/L HF presented
smaller ∂V/∂t, leading to the slow formation of the oxide
and consequently resulting in an oxide with fewer defects.
This would explain the higher density observed for the oxide
formed in the higher concentration of HF.
41
Marcolin et al.

2 Choi J, Lim JH, Lee J, Kim KJ. Porous niobium oxide films prepared by anodization– annealing–anodization.
Nanotechnology. 2007;18:055603.
3 Yao L, Wuhong X, Jiupeng Z, Xiangdong M. Fabrication and characterization of three-dimensionally ordered
macroporous niobium oxide. Solid State Sciences. 2009;11:1625-1630.
4 Kowalski D, Kim D, Schmuki P. TiO2 nanotubes, nanochannels and mesosponge: Self-organized formation and
applications. Nano Today. 2013;8(3):235-264.
5 Shi L, Gu Y, Chen L, Yang Z, Ma J, Qian Y. Synthesis and charact of superconducting NbC nanotubes. Carbon.
2005;43:195-213.
6 Tsuneta T, Toshima T, Inagaki K, Hibayama T, Tanda S, Ahlskog M, et al. Formation of metallic NbSe2 nanotubes and
nanofibers. Current Applied Physics. 2003;3:473-476.
7 Choi J, Lim JH, Lee SC, Chang JH, Kim KJ, Cho MA. Porous niobium oxide films prepared by anodization in HF/
H3PO4. Electrochimica Acta. 2006;51:5502-5507.
8 Jeong B, Jung E, Kim J. Fabrication on superhydrophobic niobium pentoxide thin films by anodization. Applied
Surface Science. 2014;307:28-32.
9 Gomes MAB, Onofre S, Juanto S, Bulhões LOS. Anodization of niobium in sulphuric acid media. Journal of Applied
Electrochemistry. 1991;21:1023-1026.
10 El-Mahdy GA. Formation and dissolution behavior of niobium oxide in phosphoric acid solutions. Thin Solid Films.
1997;307:141-147.
11 Ikonopisov S. Theory of electrical breakdown during formation of barrier anodic films. Electrochimica Acta.
1977;22:1077-1082.
12 D’Alkaine CV, de Souza LMM, Nart FC. The anodic behaviour of niobium-II. General experimental electrochemical
aspects. Corrosion Science. 1993;34:117-127.
13 Wan J, Yan X, Ding J, Wang M, Hu K. Self-organized highly ordered TiO2 nanotubes in organic aqueous system.
Materials Characterization. 2009;60:1534-1540.
14 Shi P, Cheng FT, Man HC. Improvement in corrosion resistance of NiTi by anodization in acetic acid. Materials
Letters. 2007;61:2385-2388.
15 Yang DJ, Kim HG, Cho SJ, Choi WY. Thickness–conversion ratio from titanium to TiO2 nanotubes fabricated by
anodization method. Materials Letters. 2008;62:775-779.
16 Wan J, Yan X, Ding J, Wang M, Hu K. Self-organized highly ordered TiO2 nanotubes in organic aqueous system.
Materials Characterization. 2009;60:1534-1540.
17 Narayanan R, Kwon TY, Kim KH. TiO2 nanotubes from stirred glycerol/NH4F electrolyte: roughness, wetting
behavior and adhesion for implant applications. Materials Chemistry and Physics. 2009;117:460-464.
18 Sui JH, Cai W. Formation of ZrO2 coating on the NiTi alloys for improving their surface properties. Nuclear
Instruments and Methods in Physics Research. 2006;251:402-406.

Received: 14 Dec. 2016

Accepted: 25 Apr. 2017

42 Tecnol. Metal. Mater. Miner., São Paulo, v. 15, n. 1, p. 35-42, jan./mar. 2018